Modified block copolymer

Abstract

A second-order modified block copolymer which can be obtained by reacting a first-order modified block copolymer with a second-order modifier, wherein the first-order modified block copolymer comprises a base block copolymer and a functional group-containing first-order modifier group bonded to the base block copolymer, wherein the base block copolymer comprises at least one polymer block comprised mainly of vinyl aromatic hydrocarbon monomer units and at least one polymer block comprised mainly of conjugated diene monomer units, and wherein the second-order modifier has a specific functional group which is reactive to the functional group of the first-order modifier group of the first-order modified block copolymer. A second-order modified block copolymer-containing polymer composition comprising the second-order modified block copolymer as well as a thermoplastic resin and/or a rubbery polymer.

1. A polymer composition comprising:
 1 to 99% by weight, based on the total weight of components (I-1) and (II), of (I-1) a semimodified block copolymer comprising:
 a base block copolymer comprising at least one polymer block (A) comprised mainly of vinyl aromatic hydrocarbon monomer units and at least one polymer block (B) comprised mainly of conjugated diene monomer units, the amounts of said vinyl aromatic hydrocarbon monomer units and said conjugated diene monomer units in said base block copolymer being, respectively, 5 to 95% by weight and 95 to 5% by weight, based on the total weight of said vinyl aromatic hydrocarbon monomer units and said conjugated diene monomer units, and 
 a functional group-containing first-order modifier group bonded to said base block copolymer, 
 said base block copolymer being unhydrogenated or at least partially hydrogenated, 
 wherein said semimodified block copolymer (I-1) is represented by a formula selected from the group consisting of the below-mentioned formulae (6) to (10), 
 
 99 to 1% by weight, based on the total weight of components (I-1) and (II), of (II) at least one polymer selected from the group consisting of a thermoplastic resin and a rubbery polymer, and 
 0.01 to 20 parts by weight, relative to 100 parts by weight of the total of components (I-1) and (II), of (III) a second-order modifier having a functional group which is reactive to said functional group of said first-order modifier group of said semimodified block copolymer (I-1),
                     C 2 —NR 3 -D 2 ,  (8) 
   C 2 -D 2 , and  (9) 
   E 2 -F 2   (10) 
 
 wherein: 
 A 2  represents a unit which is represented by any one of the following formulae (a-1) and (b-1): 
 
       
         
           
           
               
               
           
         
         B 2  represents a unit which is represented by the following formula (c-1): 
       
       
         
           
           
               
               
           
         
         C 2  represents a unit which is represented by any one of the following formulae (d-1) and (e-1): 
       
       
         
           
           
               
               
           
         
         D 2  represents a unit which is represented by the following formula (f-1):
   —R 8 —NHR 3 ,  (f-1) 
 
         E 2  represents a unit which is represented by the following formula (g-1):
   —R 9 —P 1 , and  (g-1) 
 
         F 2  represents a unit which is represented by any one of the following formulae (h-1) to (j-1):
   —NH—R 10 —Si(OR 11 ) 3 ,  (h-1) 
 
       
       
         
           
           
               
               
           
         
         wherein, in the formulae (6) to (8) and (a-1) to (j-1):
 N represents a nitrogen atom, Si represents a silicon atom, O represents an oxygen atom, C represents a carbon atom, and H represents a hydrogen atom, 
 P 1  represents the base block copolymer, 
 R 1a  represents a trivalent aliphatic C 1 -C 48  hydrocarbon group, 
 each of R 1b , R 4 , R 8  to R 10  and R 13  to R 20  independently represents a C 1 -C 48  alkylene group, 
 each of R 2 , R 3  and R 11  independently represents a C 1 -C 48  alkyl group, a C 6 -C 48  aryl group, an alkylaryl group comprised of C 1 -C 48  alkyl and C 6 -C 48  aryl, an aralkyl group comprised of C 1 -C 48  alkyl and C 6 -C 48  aryl, or a C 3 -C 48  cycloalkyl group, 
 wherein each of R 1a , R 1b , R 3 , R 4 , R 8  to R 10  and R 13  to R 15  optionally independently has at least one functional group selected from the group consisting of a hydroxyl group, an epoxy group, an amino group, a silanol group and a C 1 -C 24  alkoxysilane group, 
 each of R 5  to R 7  and R 12  independently represents a hydrogen atom, a C 1 -C 48  alkyl group, a C 6 -C 48  aryl group, an alkylaryl group comprised of C 1 -C 48  alkyl and C 6 -C 48  aryl, an aralkyl group comprised of C 1 -C 48  alkyl and C 6 -C 48  aryl, or a C 3 -C 48  cycloalkyl group, 
 wherein each of R 1a , R 1b , R 2  to R 4  and R 8  to R 15  optionally independently has bonded thereto at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom, said at least one atom being bonded in a form other than a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group, and 
 each of t, u, v and x is independently an integer of 0 or more, provided that both t and u are not simultaneously 0, and w is an integer of 1 or more. 
 
       
     
     
       2. The polymer composition according to  claim 1 , wherein said thermoplastic resin in component (II) is a functional group-containing thermoplastic resin and said rubbery polymer in component (II) is a functional group-containing rubbery polymer. 
     
     
       3. The polymer composition according to  claim 2 , wherein:
 said functional group-containing thermoplastic resin comprises at least one member selected from the group consisting of a polyester resin, a polyamide resin, a polycarbonate resin, a polyurethane resin, a polyphenylene ether resin and a polyoxymethylene resin, and 
 said functional group-containing rubbery polymer comprises at least one member selected from the group consisting of an olefin elastomer and a styrene elastomer each of which contains at least one functional group selected from the group consisting of an acid anhydride group, a carboxyl group, a hydroxyl group, an epoxy group and an amino group. 
 
     
     
       4. The polymer composition according to  claim 2 , wherein said functional group of said second-order modifier (III) is reactive to both said functional group of said first-order modifier group of said semimodified block copolymer (I-1) and said functional group of said component (II). 
     
     
       5. A polymer composition comprising:
 1 to 99% by weight, based on the total weight of components (I-1) and (II), of (I-1) a semimodified block copolymer comprising:
 a base block copolymer comprising at least one polymer block (A) comprised mainly of vinyl aromatic hydrocarbon monomer units and at least one polymer block (B) comprised mainly of conjugated diene monomer units, the amounts of said vinyl aromatic hydrocarbon monomer units and said conjugated diene monomer units in said base block copolymer being, respectively, 5 to 95% by weight and 95 to 5% by weight, based on the total weight of said vinyl aromatic hydrocarbon monomer units and said conjugated diene monomer units, and 
 a functional group-containing first-order modifier group bonded to said base block copolymer, 
 said base block copolvmer being unhydrogenated or at least partially hydrogenated, 
 wherein said semimodified block copolymer (I-1) is represented by a formula selected from the group consisting of the below-mentioned formulae (6) to (10), 
 
 99 to 1% by weight, based on the total weight of components (I-1) and (II), of (II) at least one nolymer selected from the group consisting of a thermoplastic resin and a rubbery polymer, and 
 0.01 to 20 parts by weight, relative to 100 parts by weight of the total of components (I-1) and (II), of (III) a second-order modifier having a functional group which is reactive to said functional group of said first-order modifier group of said semimodified block copolymer (I-1),
                     C 2 —NR 3 -D 2 ,  (8) 
   C 2 -D 2 , and  (9) 
   E 2 -F 2   (10 ) 
 
 wherein: 
 A 2  represents a unit which is represented by any one of the following formulae (a-1) and (b-1): 
 
       
         
           
           
               
               
           
         
         B 2  represents a unit which is represented by the following formula (c-1): 
       
       
         
           
           
               
               
           
         
         C 2  represents a unit which is represented by any one of the following formulae (d-1) and (e-1) 
       
       
         
           
           
               
               
           
         
         D 2  represents a unit which is represented by the following formula (f-1):
   —R 8 —NHR 3 ,  (f-1) 
 
         E 2  represents a unit which is represented by the following formula (g-1):
   —R 9 —P 1 , and 
 
         F 2  represents a unit which is represented by any one of the following formulae (h-1) to (j-1):
   —NHR—R 10 —Si(OR 11 ) 3 ,  (h-1) 
 
       
       
         
           
           
               
               
           
         
         wherein, in the formulae (6) to (8) and (a-1) to (j-1):
 N represents a nitrogen atom, Si represents a silicon atom, O represents an oxygen atom, C represents a carbon atom, and H represents a hydrogen atom, 
 P 1  represents the base block copolymer, 
 R 1a  represents a trivalent aliphatic C 1 -C 48  hydrocarbon group, 
 each of R 1b , R 4 , R 8  to R 10  and R 13  to R 20  independently represents a C 1 -C 48  alkylene group, 
 each of R 2 , R 3  and R 11  independently represents a C 1 -C 48  alkyl group, a C 6 -C 48  aryl group, an alkylaryl group comprised of C 1 -C 48  alkyl and C 6 -C 48  aryl, an aralkyl group comprised of C 1 -C 48  alkyl and C 6 -C 48  aryl, or a C 3 -C 48  cycloalkyl group, 
 wherein each of R 1a , R 1b , R 3 , R 4 , R 8  to R 10  and R 13  to R 15  optionally independently has at least one functional group selected from the group consisting of a hydroxyl group, an epoxy group, an amino group, a silanol group and a C 1 -C 24  alkoxysilane group, 
 each of R 5  to R 7  and R 12  independently represents a hydrogen atom, a C 1 -C 48  alkyl group, a C 6 -C 48  aryl group, an alkylaryl group comprised of C 1 -C 48  alkyl and C 6 -C 48  aryl, an aralkyl group comprised of C 1 -C 48  alkyl and C 6 -C 48  aryl, or a C 3 -C 48  cycloalkyl group, 
 wherein each of R 1a , R 1b , R 2  to R 4  and R 8  to R 15  optionally independently has bonded thereto at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom, said at least one atom being bonded in a form other than a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group, and 
 each of t, u, v and x is independently an integer of 0 or more, proyided that both t and u are not simultaneously 0, and w is an integer of 1 or more, 
 
         wherein said functional group of said second-order modifier (III) comprises at least one member selected from the group consisting of a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group and an alkoxysilane group. 
       
     
     
       6. A flame retardant polymer composition comprising: 100 parts by weight of the polymer composition of  claim 1 , and 10 to 2000 parts by weight of(VI) an inorganic filler. 
     
     
       7. A crosslinked product obtained by subjecting the polymer composition of  claim 1  to melt-kneading in the presence of a vulcanizing agent. 
     
     
       8. The polymer composition according to  claim 5 , wherein said functional group of said second-order modifier (III) comprises at least one member selected from the group consisting of an acid anhydride group and an epoxy group. 
     
     
       9. The polymer composition according to  claim 5 , wherein said second-order modifier (III) is at least one selected from the group consisting of maleic anhydride, itaconic anhydride, pyromellitic anhydride, cis-4-cyclohexane-1,2-dicarboxylic acid anhydride, 1,2,4,5-benzenetetracarboxylic acid dianhydride, 5-(2,5-dioxytetrahydroxyfuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, tetraglycidyl-1,3-bisaminomethyl-cyclohexane, tetraglycidyl-m-xylenediamine, diglycidylaniline, ethylene glycol diglycidyl, propylene glycol diglycidyl, terephthalic acid diglycidyl ester acrylate, tetraglycidyl-m-xylene-diamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane, diglycidylaniline, diglycidyl-o-toluidine, 4,4′-diglycidyl-diphenylmethylamine, 4,4′-diglycidyl-dibenzylmethylamine, diglycidylaminomethylcyclohexane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyldiethylethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropyldimethylphenoxysilane, γ-glycidoxypropyldiethylmethoxysilane, γ-glycidoxypropylmethyldiisopropeneoxysilane, bis(γ-glycidoxypropyl)dimethoxysilane, bis(γ-glycidoxypropyl)diethoxysilane, bis(γ-glycidoxypropyl)dipropoxysilane, bis(γ-glycidoxypropyl)dibutoxysilane, bis(γ-glycidoxypropyl)diphenoxysilane, bis(γ-glycidoxypropyl)methylmethoxysilane, bis(γ-glycidoxypropyl)methylethoxysilane, bis(γ-glycidoxypropyl)methylpropoxysilane, bis(γ-glycidoxypropyl)methylbutoxysilane, bis(γ-glycidoxypropyl)methylphenoxysilane, tris(γ-glycidoxypropyl)methoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-methacryloxyethyltriethoxysilane, bis(γ-methacryloxypropyl)dimethoxysilane, tris(γ-methacryloxypropyl)methoxysilane, β-(3,4-epoxycyclohexyl)ethyl-trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-triethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-tripropoxysilane, β-(3,4-epoxycyclohexyl)ethyl-tributoxysilane, β-(3,4-epoxycyclohexyl)ethyl-triphenoxysilane, β-(3,4-epoxycyclohexyl)propyl-trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-ethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-ethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldipropoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldibutoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldiphenoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethylmethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-diethylethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethyethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethylpropoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethylbutoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethylphenoxysilane, β-(3,4-epoxycyclohexyl)ethyl-diethylmethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldiisopropeneoxysilane and N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propane-amine.